The present invention relates to a molded part of ceramic material derived from polymers, a process for its production by pyrolysis, and a sliding element having the molded part.
The production of ceramic materials by pyrolysis of suitable polymeric organic precursors is known from numerous publications. Polysilanes, polycarbosilanes, polysilazanes, polysiloxanes or similar compounds are normally preferred as polymeric organic precursors. Examples of many such compounds may be found in a publication entitled xe2x80x9cHigh Yield Synthesis Of Si3N4/SiC Ceramic Materials by Pyrolysis of a Novel Polyorganosilazanexe2x80x9d, by Seyfert et al. in J. Am. Ceram. Soc. (1984) C-132. In that publication it is disclosed that alkylchlorosilanes can be reacted with ammonia in the presence of a strong Lewis base and used as precursors for the production of silicon nitride ceramic materials.
The pyrolysis of siloxanes is described in a publication entitled xe2x80x9cAdv. Ceramic Materialsxe2x80x9d by D. White, 2 [1] (1987) p. 45 ff., and leads in an inert gas atmosphere or in a reducing atmosphere to products containing silicon carbide (SiC).
However, a problem encountered in the production of solid molded parts of such materials was that volatile decomposition products were always released during the pyrolysis. That resulted in high porosities and a drastic shrinkage of the material accompanied by a significant increase in density.
According to the teaching of European Patent Application 0 412 428 A1, molded parts having a high density are produced by pyrolyzing a mixture of organosilicon polymer plus metallic filler. With that method a ceramic transformation accompanied by an increase in density can be achieved, leading to a reduction in the interfering porosity and a reduction in shrinkage, which is likewise unacceptably high in practice. It is possible to produce molded parts in that way by using known molding techniques for plastics materials. However, those molded parts do not have satisfactory dry-running properties enabling them to be used as sliding elements in mixed friction or dry-running applications.
Sliding elements with the best heretofore achieved dry-running properties preferably are formed of carbon graphite, for example EK 2230 grade from SGL CARBON GmbH, Meitingen, Germany, which have an SiC element as a counter-running partner. Those sliding elements can be produced as individual moldings in which running surfaces are also subjected to a final mechanical treatment. The associated production costs are substantially higher than in the case where sliding elements are produced by conventional plastics forming processes. Coal graphite materials are produced by mixing and compressing solid carbon-containing fillers that are at least partially of a graphitic nature (e.g. natural graphite, electrographite) with carbonizable binders such as pitches and resins, and then carbonizing the compressed mixtures at temperatures between 750xc2x0 C. and 1300xc2x0 C. under the exclusion of air.
Sliding rings of ceramic materials, such as for example sintered silicon carbide, are also known. However, those materials according to European Patent EP 0 685 437 B1, corresponding to U.S. Pat. No. 5,762,895, may only be used for mixed friction applications, and are based on the fact that the material has a high porosity so that the lubricating film that is normally present between the friction partners is deposited in the pores of the sliding rings and after a brief dry running the lubricating film remaining in the pores is released in order to prevent a permanent damaging dry running. Adding solid lubricants such as preferably graphite according to European Patent Application EP 0 709 352 A1, permits the coefficients of friction of the sliding rings to be improved further, though the use of sliding rings remains limited to the case of mixed friction. The problem of dry friction cannot be solved with such a material, since only the at least partial presence of a lubricating film will permit the good sliding behavior of the material. That behavior is also illustrated further by the results of a reference measurement with SiC given in Table 2.
International Publication No. WO 99/41211 describes a process for the production, from polysilazanes, of crack-free, high density ceramic molded parts based on Si/B/C/N that can be used for tribological purposes. Depending on the composition, the material of the molded parts contains incorporated deposits of various lubricating substances such as for example graphite, boron nitride, titanium oxides and titanium carbide nitride. In that connection, a crosslinked polysilazane powder is first of all compressed hot in a depression at a defined temperature that is higher than the temperature maximum in the TMA diagram of the optimally crosslinked polymer, and is then pyrolyzed. The inexpensive production processes used in plastics technology for shaping, such as for example injection molding and extrusion, cannot be used for the production of the molded parts. The polysilazanes used for the production are furthermore significantly more expensive than other polymeric organic precursors, such as in particular polysiloxanes, which thus additionally increases the production costs of the molded parts. The molded parts produced according to International Publication No. WO 99/41211 have coefficients of friction down to less than 0.1 under dry-running conditions.
It is accordingly an object of the invention to provide a molded part of ceramic material derived from polymers, a process for producing ceramic molded parts and a sliding element having a molded part, which overcome the hereinafore-mentioned disadvantages of the heretofore-known products and processes of this general type and in which the molded parts can be produced by using production methods known in plastics technology, exhibit a low shrinkage of at most 10% during production in addition to a high density of at least 85% of a theoretical value and have satisfactory dry-running properties.
A further object of the invention was to provide molded parts of a ceramic material that can be used as bearings and sliding ring seals for dry-running applications and that can be produced from inexpensive polymeric organic precursors as raw material, in particular from polysiloxanes.
Another object of the present invention is to provide a material for molded parts that is more suitable than known materials as a material for bearings and sliding ring seals in dry-running applications.
With the foregoing and other objects in view there is provided, in accordance with the invention, a molded part of a ceramic material produced by pyrolysis of polymers, comprising a composite body of a single-phase or multi-phase, amorphous, partially crystalline or crystalline matrix selected from the group consisting of silicon carbide (SiC), silicon nitride (Si3N4), silicon dioxide (SiO2) and mixtures thereof, such as for example oxycarbides, oxynitrides, carbonitrides or oxycarbonitrides. The matrix contains graphite inclusions and the ceramic material has a density of at least 85% of a theoretical value.
With the objects of the invention in view, there is also provided a process for the production of ceramic molded parts, which comprises preparing a mixture containing polymer components in an amount of 30 to 80 wt. % referred to a total weight of the mixture, fillers in an amount of 0 to 30 wt. %, and graphite in an amount of 10 to 70 wt. %. The mixture is subjected to a forming process with heating of the mixture to crosslink the polymer components and then to a pyrolysis process for producing the ceramic molded parts.
The polymer components which are used according to the invention are, in particular, polysilanes, polysiloxanes, polysilazanes or polycarbosilanes or similar compounds and mixtures thereof known in the prior art. The inexpensive polysiloxanes which are preferably used in this connection lead to oxidic phases in the matrix of the ceramic composite materials. Methylhydroxylpolysesquisiloxane with an empirical formula of (CH3)SiO1.5 and a mean molecular weight in the region of 20,000 g/mole is particularly preferably used as a polymer component according to the invention. The proportion of the polymer component in the mixture from which the ceramic molded parts according to the invention are produced is preferably 40 wt. % to 70 wt. % and particularly preferably 50 wt. % to 60 wt. %.
The fillers which are preferably used according to the invention are high density fillers such as metallic silicon, aluminum, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, titanium or elementary boron or alloys of molybdenum and silicon or of chromium and silicon. Lanthanides and/or intermetallic compounds of subgroups IV to VI of the Periodic System with boron, silicon and/or aluminum, as well as mixtures of the described fillers, may also be used. It may also be convenient to use organometallic compounds and/or precursors, such as for example alkyls, cycloalkyls, aryls, alkoxides and/or salt-like compounds, such as for example hydrides or oxides of the metals and/or intermetallic compounds, instead of the filler components. Particularly preferred fillers are boron and silicon. The fillers are preferably added to the pyrolysis mixture in finely divided form, preferably as dry powders with a mean particle size, specified as a D50 value, in a range of from 1 to 5 xcexcm, measured with a laser granulometer (type Cilas 715). Preferred amounts of the fillers have been found in practice to be in particular 5 wt. % to 25 wt. % of the mixture, in particular 10 wt. % to 20 wt. %.
The graphite that is used is preferably added in an amount of 20 wt. % to 50 wt. % of the initial mixture. The proportion of graphite is particularly preferably 30 wt. % to 40 wt. % of the mixture. The graphite being used preferably has a density in a range of from 2.0 to 2.3 g/cm3, particularly preferably from 2.1 to 2.2 g/cm3, measured with a helium pycnometer. The mean grain size (D50) of the graphite that is used is in a range of from 2 xcexcm to 16 xcexcm, preferably 3 to 7 xcexcm, measured with a laser granulometer (type Cilas 715). According to the invention, optimally suitable forms of graphite also have a good crystalline configuration, i.e. an essentially homogeneous alignment of graphite layers. Synthetic graphite, such as for example electrographite, or natural graphite, may be used for this purpose.
It has completely surprisingly been found that in the pyrolysis of the aforedescribed pyrolysis mixture, the total amount of graphite is not consumed in the formation of carbides, but instead the graphite is almost completely retained as an inclusion in the ceramic material derived from polymers. The production of the ceramic material according to the invention is carried out under the following conditions: the polymerization of the initial mixture is carried out at temperatures in a range of from 230xc2x0 to 300xc2x0 C., and the pyrolysis of the initial polymers takes place at 900xc2x0 to 1500xc2x0 C., preferably at 1000xc2x0 to 1200xc2x0 C., under an inert gas atmosphere such as argon or pure nitrogen or under a nitrogen/hydrogen mixture over a period of 30 to 60 hours. The graphite incorporated in the material may act as a highly active lubricant in the case where sliding rings or sealing discs are produced as molded parts according to the invention from ceramic materials derived from polymers and in which the conventional lubrication by externally added lubricants is missing and dry-running ensues. The aforementioned molded parts are mainly employed in the case of mixed friction, though they may also be used for pure dry running. The coefficient of friction f as a measure of the dry-running properties of the molded parts according to the invention has in general, on the basis of DIN 50322, values of less than 0.1, preferably values of less than 0.06 and particularly preferably values of less than 0.045.
With the objects of the invention in view, the ceramic materials which are derived from polymers are particularly suitable for the production of sliding elements having a sealing and/or bearing function in movable parts in pumps, compressors, general machinery and in furnace building, especially for dry-running applications.
A preferred embodiment of the ceramic materials according to the invention involves the addition of a small amount of a catalytic substance to the initial mixture that induces a polycondensation process of the polymers which are employed. A catalyst to be added to the initial mixture may be selected from platinum group metals, iron, cobalt and/or nickel, as well as in the form of organometallic compounds, precursors and salt-like compounds and mixtures thereof. In this connection their proportion in the amount of the initial mixture is less than 10%, preferably between 0.2% and 5%, and particularly preferably between 0.5% and 1%. Particularly preferred catalysts are metal acetyl acetonates such as aluminum acetyl acetonate (C15H21AlO6) and iron acetyl acetonate. The use of the catalysts leads to a lower porosity of the ceramic material according to the invention and to a lower linear shrinkage of the ceramic material during the pyrolysis process.
The ceramic materials according to the invention are characterized by a low open porosity, which is normally less than 12 vol. %, preferably less than 7 vol. % and particularly preferably less than 4 vol. %. The ceramic materials according to the invention are also characterized by a low shrinkage behavior during the pyrolysis process. The linear shrinkage is normally less than 10%, preferably less than 7% and particularly preferably less than 5%.
All processes that have generally proved suitable in ceramic technology or plastics technology may be used to shape the ceramic materials according to the invention which are derived from polymers. These processes include pressureless casting, hot press molding, injection molding, extrusion, as well as a recent innovation, laser-assisted so-called rapid prototyping.
Other features which are considered as characteristic for the invention are set forth in the appended claims.
Although the invention is described herein as embodied in a molded part of ceramic material derived from polymers, a process for producing ceramic molded parts and a sliding element having a molded part, it is nevertheless not intended to be limited to the details given, since various modifications and structural changes may be made therein without departing from the spirit of the invention and within the scope and range of equivalents of the claims.
The construction and method of operation of the invention, however, together with additional objects and advantages thereof will be best understood from the following description of specific embodiments when read in connection with the accompanying examples.